CN105826554B - A kind of niobates composite negative pole material of lithium rechargeable battery - Google Patents
A kind of niobates composite negative pole material of lithium rechargeable battery Download PDFInfo
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- CN105826554B CN105826554B CN201510008477.9A CN201510008477A CN105826554B CN 105826554 B CN105826554 B CN 105826554B CN 201510008477 A CN201510008477 A CN 201510008477A CN 105826554 B CN105826554 B CN 105826554B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of novel niobates composite negative pole material of lithium battery and preparation method thereof.The composite active substance has formula M TiNb2O7—NTi2Nb10O29The chemical composition of expression, wherein M+N=10, M, N are mass ratio.Compared with prior art, the MTiNb that method using the present invention is prepared2O7—NTi2Nb10O29There is composite material solid solution bulk properties, performance to be better than single TiNb2O7、Ti2Nb10O29Or two kinds of materials are simply mixed；The composite material is in 1.0~3.0V (vs.Li+/ Li) SEI films will not be formed in operating voltage range, it has a safety feature, there is higher reversible specific capacity, high rate performance, be the replacement Li of great potential4Ti5O12As the negative material of lithium ion battery power battery and energy-storage battery.
Description
Technical field
The present invention relates to field of lithium ion battery more particularly to it is a kind of can be as the niobates of lithium rechargeable battery
Composite negative pole material and preparation method thereof.
Background technology
The lithium rechargeable battery used as hybrid vehicle, electric vehicle or the power supply of energy storage, it is desirable that its is necessary
Reliable, fast charging and discharging and higher energy density the characteristic with long-term safety.It is widely used that use currently on the market
Carbonaceous is the lithium rechargeable battery of negative electrode active material, since the current potential of carbonaceous material opposing metallic lithium is not high, in charge and discharge
Li dendrite is easily formed in the process, it is caused to be short of in terms of fast charging and discharging performance and security reliability.Then people
It is dedicated to studying the composite oxide of metal relative to the current potential of lithium metal is high, security performance is excellent, uses it for lithium ion two
Primary cell negative material.Wherein, the composite oxides Li of titaniferous4Ti5O12Experts and scholars are received with its high security, long-life
Favor, and be gradually commercialized in lithium ion battery applications, but Li4Ti5O12There are the specific capacities of unit mass low, energy
Low density problem.Therefore a kind of suitable high security, high power capacity, high-power ion secondary battery cathode material lithium are found
Have great importance to power vehicle, hybrid vehicle and the popularization of energy storage.
In early days the study found that niobates composite oxide material is a kind of wide-band gap material, photovoltaic electrode can be applied to.Niobium
The type of hydrochlorate composite oxides is more, wherein the TiNb of monoclinic system2O7With rhombic Ti2Nb10O29, be applied to lithium from
Sub- cell negative electrode material has preferable performance.
TiNb2O7Monocline layer structure, space group C2/m, 0.1C charging/discharging voltage platform 1.64V (vs.Li+/ Li), it is embedded
5mol Li+The theoretical specific capacity 387.6mAh/g of material, embedded 4mol Li+The theoretical specific capacity 310mAh/g of material, and it is practical
Specific capacity is 280mAh/g (Xia Lu, a Zelang Jian, ab Zheng Fang, a Lin Gu, * ac Yong-Sheng
Hu,*a Wen Chen,b Zhaoxiang Wanga and Liquan Chen.Energy Environ.Sci.,2011,4,
2638.)
Nineteen fifty-five Roth and Coughanour reports TiNb for the first time2O7Material (Roth, R.S.；Coughanour,
L.W.J.Res.Natl.Bur.Stand.1955,55,209–213.).Goodenough in 2011, J.B are proposed TiNb2O7Material
Expect (Jian-Tao Han And Goodenough, J.B., Chem.Mater, 2011 (23):P.3404-3407) it is applied to lithium
In ion battery, coordinates with positive electrode after making lithium ion battery, there is higher specific capacity, excellent cycle performance.
It studies simultaneously and finds Ti2Nb10O29Material (number of patent application 201210436696.3) has rectangle structure, is applied to
Its theoretical specific capacity is 396mAh/g after lithium ion battery, is Li4Ti5O122.26 times, 1.0~3.0V of operating voltage range
(vs.Li+/ Li), SEI films will not be formed in its operating voltage range.Research finds Ti2Nb10O29(Electrochemistry
Communications 25(2012)39–42)Ti2Nb10O29) excellent high rate performance is shown, it is its opening after all
The ReO3 crystal structures of formula, are conducive to Li+Quick diffusion.
Niobates negative material TiNb2O7Or Ti2Nb10O29With commercialized lithium ion battery negative material
Li4Ti5O12It compares, except with Li4Ti5O12Safety, the long-life is outer, high power, also excellent with the larger energy storage of energy density
Gesture, so niobates composite material applies pole as negative material active material in lithium-ion-power cell and energy-storage battery
Tool foreground.
Invention content
In order to reach Li4Ti5O12The safety of battery, the characteristic of fast charging and discharging, while the energy of battery can also be improved
Density, the present invention provides a kind of novel niobates composite negative pole material as lithium secondary battery, this composite material includes
TiNb2O7And Ti2Nb10O29Two kinds of crystal structures, wherein TiNb2O7And Ti2Nb10O29The particle surface of material respectively forms
One layer contains Ti2Nb10O29And TiNb2O7Solid solution coating film；The novel niobates composite negative pole of the method synthesis of the present invention
Material property is better than single TiNb2O7、Ti2Nb10O29Or two kinds of materials are simply mixed.
The technical solution of the lithium rechargeable battery niobates composite negative pole material and preparation method thereof of the present invention is specifically such as
Under：
A kind of niobates composite negative pole material of lithium rechargeable battery, with following general formula：
MTiNb2O7—NTi2Nb10O29,
Wherein M+N=10, M, N are respectively TiNb2O7And Ti2Nb10O29Quality coefficient, that is, M：N is the quality of two materials
Than.
The material working voltage platform ranging from 1.45~1.65V (vs.Li+/Li)；The crystal structure of the material includes single
Oblique and the two kinds of crystal structures in rectangle combination；And TiNb2O7And Ti2Nb10O29The particle surface of material has been respectively formed one layer
Ti2Nb10O29With TiNb2O7Solid solution coating film.
The preparation method of the novel niobates composite negative pole material of the present invention, includes the following steps：
1) synthesis TiNb is pressed2O7Required each element molar ratio weighs raw material, and drying after dispersant is added, will dry
Material afterwards is placed in Muffle furnace, is passed through air, is raised to 900~1300 degree with 5 DEG C/min heating rates, is kept the temperature 8~24 hours,
Obtain intermediate TiNb2O7；
2) intermediate TiNb prepared by the step 1) that mass ratio is M is weighed2O7, then synthesis matter is added into the intermediate
Amount ratio is the Ti of N2Nb10O29Required raw material is added drying after the ground crushing of dispersant, gained dry mixed powder is set
In Muffle furnace, be passed through air, and be warming up to 900~1200 DEG C heat preservation 8~for 24 hours, cooled to room temperature, you can obtain niobic acid
Salt composite negative pole material MTiNb2O7—NTi2Nb10O29。
In the above synthetic method：
Raw material titanium compound used in the preparation method of the present invention is anatase titanium dioxide, unformed titanium dioxide
Or the combination of one or more of metatitanic acid；
Niobium compound used is the combination of one or more of niobium hydroxide, niobium oxalate or niobium pentaoxide；
The dispersant is the combination of one or more of water, methanol, ethyl alcohol or acetone；And mixed slurry solid content point
Not Xuan Zi 40~80wt% range；
Niobates composite negative pole material working voltage platform ranging from 1.45~1.65V (vs.Li of the present invention+/ Li), with
The 1.55V of lithium titanate material is compared, and there is solid solution bulk properties, performance to be better than single TiNb2O7、Ti2Nb10O29Or two kinds of materials
Be simply mixed；The composite material is in 1.0~3.0V (vs.Li+/ Li) SEI films will not be formed in operating voltage range, equally may be used
Solve the precipitation due to lithium metal and to form Li dendrite and cause the safety problem of battery short circuit.The material specific capacity simultaneously
Height, power-performance are good, can realize the quick charge and discharge of power battery, can meet the application of energy storage, and its synthesis technology is simple, close
It is excellent at the processing performance of material, it is suitble to industrialized production, is the replacement Li of great potential4Ti5O12It is dynamic as lithium ion battery
The negative material of power battery and energy-storage battery.
Description of the drawings
Fig. 1 is that reference example of the present invention and the XRD spectra of the niobates composite negative pole material of embodiment one compare.
Fig. 2 is niobates composite negative pole material electron microscope (SEM) photo of reference example of the present invention and embodiment two.
Fig. 3 is niobates composite negative pole material transmission microscopy electronic diffraction (STEM) photo of the embodiment of the present invention two.
Fig. 4 is reference example negative material (vs.Li of the present invention+/ Li) charging/discharging voltage under different multiplying-specific capacity is bent
Line.
Fig. 5 is the niobates composite negative pole material (vs.Li of the embodiment of the present invention two+/ Li) charge and discharge under different multiplying
Piezoelectric voltage-specific capacity curve.
Fig. 6 is the niobates composite negative pole material (vs.Li of the embodiment of the present invention four+/ Li) charge and discharge under different multiplying
Piezoelectric voltage-specific capacity curve.
Specific implementation mode
Following embodiment is to make further to lithium rechargeable battery niobates composite negative pole material proposed by the present invention
It illustrates, but is not used in the protection domain of limitation invention.
Reference example：
TiNb2O7It prepares
It is raw material to select anatase titanium dioxide, niobium pentaoxide, by synthesis TiNb2O7Each element needed for molecular formula
Molar ratio weighs, and using ethyl alcohol as dispersant, it is 60wt% to be added to slurry solid content, dries after mixing, material is placed in horse
Not in stove, it is passed through air, 1250 degree is raised to 5 DEG C/min heating rates, keeps the temperature 16 hours, obtain white product TiNb2O7。
Embodiment one：
9TiNb2O7—1Ti2Nb10O29It prepares
It is raw material to select anatase titanium dioxide, niobium pentaoxide first, by the TiNb of synthesis 90g2O7Needed for molecular formula
Each element molar ratio weigh, using ethyl alcohol as dispersant, slurry solid content be 60wt%, dry after mixing, material be placed in
In Muffle furnace, it is passed through air, 1250 degree is raised to 5 DEG C/min heating rates, keeps the temperature 16 hours, obtain white TiNb2O7Matrix；And
It is raw material to select anatase titanium dioxide, niobium hydroxide afterwards, by the molecular formula TiNb of synthetic product2O7：Ti2Nb10O29=9:1
(mass ratio), to the TiNb of manufactured 90g2O7The Ti of synthesis 10g is added in matrix2Nb10O29The raw material of required ratio, with ethyl alcohol
For dispersant, slurry solid content is that material is placed in Muffle furnace by 40wt% after combination drying, is passed through air, with 5 DEG C/
Min heating rates are raised to 1100 degree, keep the temperature 8 hours, niobates composite negative pole material is can be obtained after cooled to room temperature
9TiNb2O7—1Ti2Nb10O29(100g)。
Embodiment two：
8.3TiNb2O7—1.7Ti2Nb10O29Preparation
It is raw material to select anatase titanium dioxide, niobium hydroxide first, by the TiNb of synthesis 83kg2O7Needed for molecular formula
Each element molar ratio weigh, using ethyl alcohol as dispersant, slurry solid content be 50wt%, dry after mixing, material be placed in
In Muffle furnace, it is passed through air, 1200 degree is raised to 5 DEG C/min heating rates, keeps the temperature 12 hours, obtain TiNb2O7Matrix；Then select
It is raw material with anatase titanium dioxide, niobium hydroxide, by the molecular formula TiNb of synthetic product2O7：Ti2Nb10O29=8.3:1.7
(mass ratio), to the TiNb of 83kg2O7The Ti of synthesis 17kg is added in matrix2Nb10O29The raw material of required ratio is point with methanol
Powder, slurry solid content are that material is placed in Muffle furnace by 60wt% after combination drying, air are passed through, with 5 DEG C/min liters
Warm speed is raised to 1000 degree, keeps the temperature 8 hours, niobates composite negative pole material is can be obtained after cooled to room temperature
8TiNb2O7—2Ti2Nb10O29(100kg)。
Embodiment three：
5TiNb2O7—5Ti2Nb10O29Preparation
It is raw material to select metatitanic acid, niobium pentaoxide first, by the TiNb of synthesis 500g2O7Each element needed for molecular formula
Molar ratio weighs, and using methanol as dispersant, slurry solid content is 60wt%, dries after mixing, material is placed in Muffle furnace,
It is passed through air, 1200 degree is raised to 5 DEG C/min heating rates, keeps the temperature 24 hours, obtain TiNb2O7Matrix；Then select Detitanium-ore-type
Titanium dioxide, niobium hydroxide are raw material, by the molecular formula TiNb of synthetic product2O7：Ti2Nb10O29=5:5 (mass ratioes), to
The TiNb of 500g2O7The Ti of synthesis 500g is added in matrix2Nb10O29The raw material of required ratio, using ethyl alcohol as dispersant, slurry is solid
Content is 50wt%, and after combination drying, material is placed in Muffle furnace, is passed through air, is raised to 5 DEG C/min heating rates
1100 degree, 12 hours are kept the temperature, niobates composite negative pole material 5TiNb is can be obtained after cooled to room temperature2O7—
5Ti2Nb10O29(1kg)。
Example IV：
2TiNb2O7—8Ti2Nb10O29Preparation
It is raw material to select anatase titanium dioxide, niobium oxalate first, by the TiNb of synthesis 20kg2O7Needed for molecular formula
Each element molar ratio weighs, and using ethyl alcohol as dispersant, slurry solid content is 40wt%, dries after mixing, material is placed in horse
Not in stove, it is passed through air, 1150 degree is raised to 5 DEG C/min heating rates, keeps the temperature 12 hours, obtain TiNb2O7Matrix；Then select
Anatase titanium dioxide, niobium hydroxide are raw material, by synthesis of product molecules formula TiNb2O7：Ti2Nb10O29=2:8 (quality
Than), to the TiNb of 20kg2O7The Ti of synthesis 80kg is added in matrix2Nb10O29The raw material of required ratio, using ethyl alcohol as dispersant,
Slurry solid content is that material is placed in Muffle furnace by 40wt% after combination drying, air is passed through, with 5 DEG C/min heating rates
1100 degree are raised to, 8 hours is kept the temperature, niobates composite negative pole material 2TiNb is can be obtained after cooled to room temperature2O7—
8Ti2Nb10O29(100kg)。
Following table 1 is object phase composition and the chemical property table of reference example of the present invention and each embodiment.
Table 1
Claims (7)
1. a kind of preparation method of the niobates composite negative pole material of lithium rechargeable battery, includes the following steps：
1) synthesis TiNb is pressed2O7Required each element molar ratio weighs raw material, drying after dispersant is added, by object after drying
Material is placed in Muffle furnace, is passed through air, is raised to 900~1300 degree with 5 DEG C/min heating rates, is kept the temperature 8~24 hours, obtain intermediate
Body TiNb2O7；
2) the intermediate TiNb that mass ratio is M is weighed2O7, then the Ti for synthesizing that mass ratio is N is added to it2Nb10O29Required
Raw material is added drying after the ground crushing of dispersant, then gained dry mixed powder is placed in Muffle furnace, is passed through air, and
Be warming up to 900~1200 DEG C heat preservation 8~for 24 hours, cooled to room temperature is to get niobates composite negative pole material MTiNb2O7—
NTi2Nb10O29；
Wherein, M+N=10, M：N is TiNb2O7And Ti2Nb10O29Mass ratio.
2. the preparation method described in claim 1, it is characterised in that in the step (1) and step (2), titanizing used is closed
Object is the combination of one or more of anatase titanium dioxide, unformed titanium dioxide or metatitanic acid.
3. the preparation method described in claim 1, it is characterised in that in the step (1) and step (2), niobium chemical combination used
Object is the combination of one or more of niobium hydroxide, niobium oxalate or niobium pentaoxide.
4. the preparation method described in claim 1, it is characterised in that in the step (1), (2), dispersant used be water,
The combination of one or more of methanol, ethyl alcohol or acetone, and mixed slurry solid content is selected from the range of 40~80wt%.
5. a kind of niobates Compound Negative of the lithium rechargeable battery prepared according to any preparation methods of claim 1-4
Pole material, it is characterised in that the material has following general formula：
MTiNb2O7—NTi2Nb10O29,
Wherein M+N=10, M：N is TiNb2O7And Ti2Nb10O29Mass ratio.
6. the niobates composite negative pole material of lithium rechargeable battery according to claim 5, it is characterised in that the material
To Li+1.45~1.65V of/Li voltage platforms.
7. according to the niobates composite negative pole material of the lithium rechargeable battery described in claim 5, it is characterised in that the material
For the crystal structure of material there are two-phase, the first phase is monoclinic system, and the second phase is orthorhombic system.
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| JP6933597B2 (en) * | 2018-03-16 | 2021-09-08 | 株式会社東芝 | Negative electrode active material for secondary batteries, electrodes, secondary batteries, battery packs, and vehicles |
| JP6937262B2 (en) * | 2018-03-23 | 2021-09-22 | 株式会社東芝 | Active materials, electrodes, rechargeable batteries, battery packs, and vehicles |
| CN109119630B (en) * | 2018-08-30 | 2021-08-13 | 陕西科技大学 | Tin niobate nanocrystal, preparation method thereof and application thereof in preparation of lithium battery |
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| CN101794905A (en) * | 2010-01-19 | 2010-08-04 | 北京中科空海新能源科技有限责任公司 | Energy storage device and manufacturing method thereof |
| CN102983316A (en) * | 2012-11-05 | 2013-03-20 | 华中科技大学 | Electrode material of secondary lithium ion battery, and its preparation method |
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| CN101794905A (en) * | 2010-01-19 | 2010-08-04 | 北京中科空海新能源科技有限责任公司 | Energy storage device and manufacturing method thereof |
| CN102983316A (en) * | 2012-11-05 | 2013-03-20 | 华中科技大学 | Electrode material of secondary lithium ion battery, and its preparation method |
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